Water soluble basic dyestuffs

ABSTRACT

Basic dyestuffs of the formula ##STR1## or tautomeric forms thereof, wherein 
     R 1  and R 2  stand for hydrogen, C 1  -C 4  -alkyl, C 1  -C 4  -alkoxy or halogen, 
     Q - E stands for C-S, C-O, C-NH or N.sup.⊕ -N.sup.⊖, 
     A stands for C 1  -C 4  -alkylene, 
     W stands for the radical of an aliphatic mono-, di-, tri-, tetra-, penta-, hexa- or heptamine, which can be protonated or quaternized, 
     n stands for 0 to 1.5 and 
     p stands for 1.3 to 10, 
     are suitable for dyeing materials which can be dyed with basic dyestuffs.

The invention relates to basic dyestuffs of the formula ##STR2## ortautomeric forms thereof, R₁ and R₂ stand for hydrogen, C₁ -C₄ -alkyl,

C₁ -C₄ -alkoxy or halogen,

Q - E stands for C-S, C-O, C-NH or N.sup.⊕ -N.sup.⊖,

A stands for C₁ -C₄ -alkylene,

W stands for the radical of an aliphatic mono-, di-, tri-, tetra-,penta-, hexa- or heptamine, which can be protonated or quaternized,

n stands for 0 to 1.5 and

p stands for 1.3 to 10,

their preparation and their use for dyeing materials which can be dyedwith basic dyestuffs.

Halogen preferably stands for chlorine or bromine.

W preferably stands for the radical ##STR3## wherein m denotes 0, 1, 2or 3,

q and r denote 0 or 1,

s denotes 0, 1 or 2,

x denotes 0, 1, 2 or 3,

B₁ and B₂ denote C₂ - or C₃ -alkylene,

B₃ denotes C₂ -C₆ -alkylene or C₄ -C₁₀ -alkylene, which is interruptedby 1 to 3 oxygens, and

R₃ to R₇ denote hydrogen, C₁ -C₄ -alkyl or C₂ -C₄ -alkyl which issubstituted by OH or C₁ -C₄ -alkoxy, or

R₄ and R₅ or - if m+q+r+s=0 -

R₅ and R₇ are closed to form a 5- or 6-membered ring,

R₈ denotes methyl, ethyl, hydroxyethyl or hydroxypropyl and

An denotes the equivalents of an anion which compensate the charge x(+). Preferred 5- or 6-membered rings are ##STR4## wherein R₉ ishydrogen, C₁ -C₄ -alkyl or C₂ -C₄ -alkyl which is substituted by OH, NH₂or C₁ -C₄ -alkoxy.

Possible anions An are all the organic and inorganic anions customaryfor cationic dyestuffs. Colourless anions are preferred.

The anion is in general determined by the preparation process and thepurification possibly carried out on the starting substances. However,the anions can also be exchanged for other anions in a known manner.Examples of An which may be mentioned are: halides, such as chloride,bromide and iodide; and sulphate, bisulphate, methylsulphate,ethylsulphate, amidosulphate, perchlorate, phosphate, hydroxide,formate, acetate, propionate, oxalate, malonate, succinate, maleate,chloroacetate, trichloroacetate, hydroxyacetate, methoxyacetate,ethoxyacetate, lactate, citrate, benzoate, methanesulphonate,ethanesulphonate, benzenesulphonate, p-toluenesulphonate, carbonate,tetrachlorozincate and tetrafluoroborate.

Preferred dyestuffs of the formula (I) are those of the formula ##STR5##or tautomeric forms thereof, wherein

R₁ ' stands for hydrogen, methoxy, ethoxy or chlorine,

R₂ ' stands for hydrogen, methyl, ethyl, methoxy or ethoxy,

p' stands for 1.5 to 6 and

W' stands for ##STR6## wherein R₅ ' is methyl, ethyl, n-propyl or --CH₂--CH₂ --OH and

R₇ ' is hydrogen, methyl, ethyl, n-propyl or --CH₂ --CH₂ --OH, ##STR7##wherein R₉ ' is methyl, ethyl, --CH₂ --CH₂ --OH or --CH₂ --CH₂ --NH₂,

3. --NH-B₃ '--NH₂

wherein

B₃ ' is ethylene, propylene, trimethylene, hexamethylene or --(CH₂)₃-O--CH₂ --CH₂ --O--(CH₂)₃ --, ##STR8## wherein B₁ ' is ethylene ortrimethylene,

R₄ ' is hydrogen, methyl, ethyl, n-propyl or --CH₂ --CH₂ --OH or

NR₄ 'R₅ ' stands for one of the following rings: ##STR9## R₁₀ ishydrogen, methyl or ethyl, ##STR10## wherein t=1, 2, 3, 4 or 5,

s+t=2, 3, 4 or 5 and

B₂ '=ethylene, propylene or trimethylene, ##STR11## wherein R₁₁ -methylor ethyl, ##STR12## and Q-E and n have the meaning given under formula(I).

Particularly preferred dyestuffs are basic dyestuffs of the formula##STR13## or tautomeric forms thereof, wherein

R₂ " stands for hydrogen or methyl,

n' stands for 0.2 to 1.2 and

W' and p' have the meaning given under formula (II).

Dyestuffs of the formula (III) which may be singled out are those of theformula ##STR14## or tautomeric forms thereof, wherein

W" stands for the following radicals ##STR15## wherein B₂ " is ethyleneor propylene,

t' is 2, 3 or 4 and

s+t' is 3 or 4 and

n" stands for 0.4 to 0.9 and

p" stands for 2 to 5.

The invention also relates to a process for the preparation of dyestuffsof the formula (I), which is characterized in that a compound of theformula ##STR16## is reacted with an amine of the formula

    HW                                                         (VI)

or with mixtures of amines of this formula, in an aqueous-alkalinemedium. The symbols used in the formulae (V) and (VI) here have themeaning given under formula (I).

A preferred process for the preparation of dyestuffs of the formula(III) is characterized in that a compound of the formula ##STR17## isreacted with an amine of the formula

    HW'                                                        (VIII)

or with mixtures of amines of this formula, in water at pH 9-12,preferably pH 10.0 to 11.5, and a temperature of 20°-100° C., preferably35°-70° C. The symbols W' and R₂ " and n' here have the meanings givenunder the formulae (II) and (III).

The pH is maintained by addition of an alkaline agent, in particular analkali metal hydroxide, such as sodium hydroxide or potassium hydroxide.

In the process according to the invention, the dyestuffs are isolated bylowering the pH to 5-9, preferably to 6-8, when the reaction has endedand before the mixture is filtered with suction. The solids can be driedor can be processed in the form of their moist press-cakes to giveliquid formulations.

The invention furthermore relates to a process for the preparation ofcompounds of the formula (V) by reaction of a chromophore of the formula##STR18## with paraformaldehyde and an amide of the formula

    H.sub.2 N-CO-alkylene-halogen                              (X)

in high-strength sulphuric or phosphoric acid or in polyphosphoric acid,if appropriate with the addition of dehydrating agents, such as sulphurtrioxide (oleum), phosphorus pentoxide, acetic anhydride or benzene- ortoluenesulphonic acid, at 0° to 140° C.

A preferred process is that in which paraformaldehyde and an amide ofthe formula (X) are first reacted in 96 to 100% strength sulphuric acidor up to 10% strength oleum at 0° to 60° C., a chromophore of theformula (IX) is then added and the subsequent reaction is carried out at0° to 140° C.

A preferred process for the preparation of compounds of the formula(VII) is that in which paraformaldehyde and 2-chloroacetamide are firstreacted in 98 to 100% strength sulphuric acid or up to 3% strength oleumat 15°-40° C., a chromophore of the formula ##STR19## wherein R₂ "stands for hydrogen or methyl as mentioned above, is then introducedinto the solution formed and the subsequent reaction is carried out at0° to 80° C. It is advantageous here initially to start at 0° to 5° C.and only later to increase the temperature.

In comparison with the conventional process for the preparation ofprecursors of the formula (V), in which a chromophore of the formula(IX) is reacted with an N-methylolamide of the formula

    HO-CH.sub.2 -NH-CO-alkylene-halogen                        (XII)

the process according to the invention has the advantage that in it theformation of the N-methylolamide of the formula (XII) and its reactionwith the chromophore of the formula (IX) can be carried out in onestage. Surprisingly, no troublesome side reactions which impair thequality of the product in comparison with the conventional process occurin this one-pot reaction according to the invention.

The dyestuffs obtained by the routes described can be used as readilywater-soluble dyestuffs from aqueous-acid solution for dyeing the mostdiverse materials, such as cellulose materials, polyacrylonitrile,acid-modified polyamide and polyester, wool and leather.

The dyestuffs according to the invention are above all outstandinglysuitable for dyeing the most diverse types of paper in clear yellowshades.

During dyeing, high degrees of exhaustion are achieved, which can berecognized by the low pollution of the effluent with dyestuff. Thedyeings have good to very good light- and wet-fastness properties. Theyare very stable towards the action of water, alcohols, soaps or aqueousorganic acids.

EXAMPLE 1

19.8 g of paraformaldehyde and then 61.5 g of chloroacetamide areintroduced into 350 ml of monohydrate (=100% strength sulphuric acid) atroom temperature, with cooling. After the mixture has been subsequentlystirred for 2 hours, it is cooled to 0° C. 100 g of the compound##STR20## are introduced at 0°-5° C., with cooling. The mixture isstirred at 0°-5° C. for a further 2 hours and is allowed to come to roomtemperature, and stirring is continued overnight. The mixture is thenheated and stirred at 60° C. for 4 hours. After cooling, the mixture isextracted by stirring on ice and the product is filtered off withsuction and washed neutral with water. 560 g of a moist filter cake areobtained, corresponding to 151 g of dry product of the formula ##STR21##

Elemental analysis of a sample dried at 60° showed 11.1% of chlorine.

λ_(max) (dimethylformamide) 412 nm.

The same result is achieved if first chloroacetamide and thenparaformaldehyde or a mixture of the two substances are introduced intosulphuric acid.

EXAMPLE 2

If the procedure is as in Example 1 but 15 g of paraformaldehyde and 47g of chloroacetamide are used, 620 g of moist goods corresponding to 150g of dry product of the formula ##STR22## are obtained.

Elemental analysis: 9.9% of chlorine and 6.1% of sulphur λ_(max)(dimethylformamide) 412 nm

EXAMPLE 3

If the procedure is as in Example 1 but 12 g of paraformaldehyde and 37g of chloroacetamide are used, 706 g of moist goods corresponding to 131g of dry product of the formula ##STR23## are obtained.

Elemental analysis: 8.8% of chlorine and 6.3% of sulphur λ_(max)(dimethylformamide) 411 nm

EXAMPLE 4

The product of the above example is also obtained if 100 g of thecompound ##STR24## and 45 g of N-methylolchloroacetamide are introducedas a mixture into 500 ml of 2% strength oleum at 0°-5° C. and themixture is subsequently stirred at this temperature for 2 hours. Afterstirring overnight at room temperature, the solution is heated brieflyto 120° C., cooled and worked up as in Example 1.

EXAMPLE 5

If the procedure is as in Example 4 but only 40 g ofN-methylolchloroacetamide are used, 120 g of the compound ##STR25##elemental analysis of which shows 7.3% of chlorine and 6.7% of sulphur,are obtained.

λ_(max) (dimethylformamide) 410 nm

EXAMPLE 6

The same product as in Example 5 is obtained if the procedure accordingto Example 1 is followed but only 10 g of paraformaldehyde and 31 g ofchloroacetamide are used.

EXAMPLE 7

371 g of the moist filter cake from Example 1 are introduced into 2.7 1of water. 37 g of 3-amino-1-methylaminopropane are added and the mixtureis heated up to 45° C., the pH being kept at 11 by addition of 1N NaOH.The mixture is stirred at 45° C. until the pH is constant. After afurther 3 hours, the pH is brought to 6.5 with dilute hydrochloric acidand the mixture is heated to 80° C., stirred until cold and filteredwith suction. The product is washed with demineralized water until freefrom chloride to give 242 g of moist goods. After drying at 60°, 94 g ofa compound of the formula ##STR26## are obtained therefrom.

The linkage isomer (amine-chromophore bond via the primary amino group)and bridged products (linkage of two chromophores via an amine) occur assecondary components. The compound dyes paper a somewhat reddish-tingedyellow, λ_(max) (20% strength acetic acid) 410 nm.

EXAMPLE 8

471 g of the moist filter cake from Example 2 are introduced into 3.1 1of water. 39 g of 3-amino-1-methylaminopropane are added and the mixtureis heated to 40° C., the pH thereby being kept at 10.5. After 1 hour,the pH is brought to 11 and the mixture is kept at 40° until the pHremains constant. If the procedure is now as described in Example 7,drying gives 115 g of a product in which the compound of the formula##STR27## is the main component. This product dyes paper a somewhatreddish-tinged yellow.

EXAMPLE 9

296 g of the moist filter cake from Example 3 are introduced into 1.9 1of water at room temperature. 14.5 g of 3-amino-1-methylaminopropane areadded and the mixture is heated up to 60° C., the pH being kept at 10.5by addition of 1N NaOH. When the pH no longer changes, after about 4hours, the pH is brought to 7 with half-concentrated hydrochloric acidand the mixture is heated to 80° C. and kept at this temperature for 1hour. The product is filtered off hot with suction, washed free fromchloride and dried at 60° C. 54 g of the dyestuff with a main componentof the formula ##STR28## are obtained.

λ_(max) (20% strength acetic acid) 408 nm.

EXAMPLE 10

296 g of the moist filter cake from Example 3 are introduced into 1.9 1of water at room temperature. 44 g of 3-amino-1-dimethylaminopropane areadded and the subsequent procedure is as in Example 9. Drying gives 51 gof the dyestuff of the formula ##STR29##

λ_(max) (20% strength acetic acid) 409 nm.

EXAMPLE 11

If the procedure is as in Example 10 but only 16.5 g of3-amino-1-dimethylaminopropane are used, 51 g of the dyestuff of theformula ##STR30## are obtained.

λ_(max) (20% strength acetic acid) 404 nm.

EXAMPLE 12

30 g of the compound from Example 5 or 6 are dissolved in 50 ml of3-amino-1-dimethylaminopropane at room temperature. The solution isconcentrated in vacuo at 50°-60° and the yellow oil which remains isconverted into a powder by digestion with acetone. This powder isfiltered off with suction and rinsed with acetone. Drying at 60° gives34 g of the dyestuff of the formula ##STR31##

λ_(max) (20% strength acetic acid) 412 nm.

In the following examples, the precursor from Example 1 is reacted inaccordance with Example 7 with the amounts shown in Table 1 of theamines listed therein instead of with 37 g of3-amino-1-methylaminopropane. The products thus obtained contain as themain component dyestuffs of the general formula ##STR32## wherein Xstands for a monovalent radical of the amines listed.

The dyestuffs dye paper a somewhat reddish-tinged yellow. Mixtures ofthe amines mentioned in the examples can also be used in order to obtaindyestuffs of the above formula.

                  TABLE 1    ______________________________________                                   g      g    Examples           Amine                   used   yield    ______________________________________    13     H.sub.2 N(CH.sub.2CH.sub.2(NH) .sub.3H                                   60     92    14     H.sub.2 N(CH.sub.2CH.sub.2NH) .sub.4H                                   77     90    15     tripropylenetetramine   79     93    16     H.sub.2 N(CH.sub.2).sub.3NHC.sub.2 H.sub.5                                   43     95    17     H.sub.2 NCH.sub.2CH.sub.2N(C.sub.2 H.sub.5).sub.2                                   49     95    18            ##STR33##              54     94    19     H.sub.2 N(CH.sub.2).sub.3N(CH.sub.3).sub.2                                   43     93    20     H.sub.2 N(CH.sub.2).sub.3N(C.sub.2 H.sub.5).sub.2                                   54     94    21     (H.sub.2 NCH.sub.2CH.sub.2CH.sub.2 ) .sub.2NCH.sub.3                                   59     91    22            ##STR34##              61     96    23     H.sub.2 N(CH.sub.2).sub.3NCH.sub.3CH.sub.2CH.sub.2 OH                                   55     95    24     H.sub.2 N(CH.sub.2).sub.3N(CH.sub.2CH.sub.2OH).sub.2                                   67     95    25     H.sub.2 N(CH.sub.2).sub.3NHCH.sub.2CH.sub.2OH                                   50     91    26     (H.sub.2 NCH.sub.2CH.sub.2CH.sub.2 ) .sub.2NH                                   55     93    27     H.sub.2 NCH.sub.2CHCH.sub.3NH.sub.2                                   31     96    28            ##STR35##              36     94    29     (CH.sub.3NHCH.sub.2CH.sub.2).sub.2 NCH.sub.3                                   61     95    30     H.sub.2 NCH.sub.2CH.sub.2NH.sub.2                                   25     91    ______________________________________

In the following examples, the precursor from Example 2 is reacted inaccordance with Example 8 with the amounts shown in Table 2 of theamines listed therein instead of with 39 g of3-amino-1-methylaminopropane. The products thus obtained contain as themain component dyestuffs of the general formula ##STR36## wherein Xstands for a monovalent radical of the amines listed.

The dyestuffs dye paper a somewhat reddish-tinged yellow. Mixtures ofthe amines mentioned in the examples can also be used in order to obtaindyestuffs of the above formula.

                  TABLE 2    ______________________________________    Examples           Amine                 g used  g yield    ______________________________________    31     H.sub.2 NCH.sub.2CH.sub.2N(C.sub.2 H.sub.5).sub.2                                 51      116    32     H.sub.2 N(CH.sub.2CH.sub.2NH).sub.2H                                 45      116    33     H.sub.2 N(CH.sub.2CH.sub.2NH).sub.3H                                 62      117    34     H.sub.2 N(CH.sub.2CH.sub.2NH).sub.4H                                 78      111    35     dipropylenetriamine   56      114    36     tripropylenetriamine  80      110    37     H.sub.2 N(CH.sub.2).sub.3N(CH.sub.3).sub.2                                 45      114    38     [(CH.sub.3).sub.2 NCH.sub.2CH.sub.2CH.sub.2 ] .sub.2NH                                 80      113    39     (H.sub.2 NCH.sub.2CH.sub.2CH.sub.2).sub.2NCH.sub.3                                 61      115    40     H.sub.2 N(CH.sub.2).sub.6NH.sub.2                                 51      109    41            ##STR37##            57      110    42     H.sub.2 N(CH.sub.2).sub.3NHC.sub.2 H.sub.5                                 45      116    43            ##STR38##            63      117    44     HN(CH.sub.3).sub.2    20      109    45            ##STR39##            38      111    46            ##STR40##            31      109    47     H.sub.2 NCH.sub.2CH.sub.2NH.sub.2                                 27      112    ______________________________________

In the following examples, the precursor from Example 3 is reacted inaccordance with Example 9 with the amounts shown in Table 3 of theamines listed therein instead of with 14.5 g of3-amine-1-methylaminopropane. The products thus obtained contain as themain component dyestuffs of the general formula ##STR41## wherein Xstands for a monovalent radical of the amines listed.

Mixtures of the amines mentioned in the examples can also be used. Thedyestuffs dye paper a somewhat reddish-tinged yellow.

                  TABLE 3    ______________________________________                                   g      g    Examples           Amine                   used   yield    ______________________________________    48     H.sub.2 N(CH.sub.2CH.sub.2NH).sub.4H                                   28     54    49     H.sub.2 N(CH.sub.2CH.sub.2NH).sub.5H                                   35     55    50     CH.sub.3NH(CH.sub.2CH.sub.2NH).sub.2CH.sub.3                                   28     54    51     (H.sub.2 N(CH.sub.2).sub.3NCH.sub.3CH.sub.2).sub.2                                   31     53    52     (H.sub.2 N(CH.sub.2).sub.3OCH.sub.2).sub.2                                   27     54    53     (H.sub.2 N(CH.sub.2).sub.3NHCH.sub.2).sub.2                                   27     54    54            ##STR42##              20     55    55     Tripropylentetramin     28     53    56     (H.sub.2 NCH.sub.2CH.sub.2CH.sub.2).sub.2NCH.sub.3                                   23     54    57     [(CH.sub.3).sub.2 N CH.sub.2CH.sub.2CH.sub.2 ].sub.2NH                                   28     55    58     H.sub.2 N(CH.sub.2).sub.3NHCH.sub.2CH.sub.2NH.sub.2                                   19 52    ______________________________________

In the following examples, the amounts listed in Table 4 of thechromophoric compounds of the general formula ##STR43## are reacted inaccordance with Example 1 with 15 g of paraformaldehyde and 47 g ofchloroacetamide. Dyestuff precursors of the general formula ##STR44##the yields of which are also shown in the table, are

                  TABLE 4    ______________________________________    Ex-    ample           Ar           g used  g yield    ______________________________________    59           ##STR45##             96      138    60           ##STR46##             92      126    61           ##STR47##             92      128    62           ##STR48##             96      131    63           ##STR49##             96      133    64           ##STR50##             100     116    ______________________________________

EXAMPLE 65

111 g of the product from Example 59 are reacted with 56 g ofN-(2-aminoethyl)-piperazine in 3.2 l of water in accordance with Example8. 113 g of a product with a main component of the formula ##STR51## arethus obtained.

The product dyes paper a neutral yellow.

EXAMPLE 66

107 g of the product from Example 60 are reacted with 62 g of (H₂ N--CH₂--CH₂ --CH₂)₂ N--CH₃ in 2 l of water in accordance with Example 8. 107 gof a product with a main component of the formula ##STR52## are thusobtained.

The product dyes paper a somewhat greenish-tinged yellow.

EXAMPLE 67

If the procedure is as in the above example but the compound fromExample 61 is used as the educt instead of that from Example 60, 109 gof a product with a main component of the formula ##STR53## areobtained.

The product dyes paper a neutral yellow.

EXAMPLE 68

110 g of the compound from Example 62 are reacted with 62 g ofN-(3-aminopropyl)-morpholine in 2 l of water in accordance with Example8, whereupon 109 g of a product of the formula ##STR54## which dyespaper a neutral yellow are obtained.

EXAMPLE 69

If the procedures is as in the above example but the compound fromExample 63 is used as the educt instead of that from Example 62, 110 ofa product of the formula ##STR55## which dyes paper a somewhatgreenish-tinged yellow are obtained.

EXAMPLE 70

116 g of the product from Example 64 are introduced into 3 l of water atroom temperature and the mixture is heated to 40° C. 58 g of3-amino-1-diethylaminopropane are added all at once and the pH is keptat 11 by addition of aqueous KOH solution. The temperature is increasedto 70° in the course of 6 hours, the pH is then brought to 6 by additionof dilute sulphuric acid and the mixture is filtered with suction. Theproduct is washed neutral and dried to give 112 g of the dyestuff of thefollowing formula, which dyes paper a reddish-tinged yellow. ##STR56##

EXAMPLE 71

A mixture of 12 g of paraformaldehyde and 43 g of 3-chloropropionamideis introduced into 300 ml of monohydrate at room temperature, withcooling. The mixture is then kept at 30° C. for 1 hour and cooled to 0°to 5° C. and 100 g of the compound ##STR57## are slowly introduced. Ifthe procedure is otherwise as in Example 1, drying gives 141 g of thecompound ##STR58## Elemental analysis 80% of chlorine.

The use of the equimolar amount of 3-bromopropionamide leads to theanalogous bromine compound.

EXAMPLE 72

55 g of the compound from Example 71 are introduced into 1.5 l of water,16.5 g of 3-amino-1-dimethylaminopropane are added and the pH is kept at10.7 by addition of sodium carbonate. The mixture is thereby heated to60°. When the pH remains constant, after about 5 hours, the pH is slowlybrought to 7 with concentrated hydrochloric acid, the mixture issubsequently stirred at 80° C. for 1 hour and the product is filteredoff hot with suction. Washing until free from salts and drying at 60° C.gives 52 g of a dyestuff of the formula ##STR59## which dyes paper asomewhat reddish-tinged yellow.

λ_(max) (20% strength acetic acid) 411 nm.

EXAMPLE 73

If the procedure is as in Example 7 but 93 g of 54% strength aqueousdimethylamine solution are used as the amine, drying gives 91 g of acompound of the formula ##STR60## which dyes paper a somewhatreddish-tinged yellow.

EXAMPLE 74

The product from Example 11 is suspended in the form of its moistpress-cake, without prior drying, in 1 l of water. 17 ml of dimethylsulphate are added and the pH is kept at 9 at room temperature byaddition of 1 N NaOH solution. After 2 hours, the mixture is heated to40° C. and is thereby still kept at pH 9. After a further 2 hours, thepH is brought to 65. with dilute hydrochloric acid and the mixture isheated to 80° C. and filtered with suction. Washing until free fromsalts and drying gives 54 g of a dyestuff of the formula ##STR61## whichdyes paper a somewhat reddish-tinged yellow.

We claim:
 1. A basic dyestuff of the formula ##STR62## or tautomericforms thereof, whereinR₁ and R₂ stand for hydrogen C₁ -C₄ -alkyl, C₁ -C₄-alkoxy or halogen, Q--E stands for C--S, C--O, C--NJ or N.sup.⊕ -N⁶³ ,A stands for C₁ -C₄ -alkylene, n stands for 0 to 1.5 and p stands for1.3 to 10, and W stands for 1) ##STR63## wherein B is ethylene ortrimethylene, R₄ and R₅ together with the N to which they are attachedare ##STR64## R₉ is methyl, ethyl, CH₂ CH₂ OH or CH₂ CH₂ NH₂, and R₁₀ isH, methyl or ethyl; ##STR65## wherein B₂ is ethylene, propylene ortrimethylene, t is 1,2,3,3 or 5 ands+t is 2,3,4 or 5 ##STR66## whereinR₁₁ is methyl or ethyl; whereinR₁₁ is methyl or ethyl; ##STR67## whereinr is 0 or 1 ##STR68##
 2. A basic dyestuff according to claim 1, of theformula ##STR69## or a tautomeric form thereof, whereinR₁ ' stands forhydrogen, methoxy, ethoxy or chlorine, R₂ ' stands for hydrogen, methyl,ethyl, methoxy or ethoxy, p' stands for 1.5 to
 6. 3. A basic dyestuffaccording to claim 1 of the formula ##STR70## or a tautomeric formthereof, whereinW" stands for the following radicals, ##STR71## whereinB₂ " is ethylene or propylene, t' is 2, 3 or 4 and s+t' is 3 or 4 and n"stands for 0.4 to 0.9 and p" stands for 2 to
 5. 4. A dyestuff accordingto claim 3, of the formula ##STR72## or tautomeric forms thereof,whereinR₂ " stands for hydrogen or methyl, n' stands for 0.2 to 1.2.